Title of Invention

COPOLYMERS BASED ON UNSATURATED MONO-OR DICARBOXYLIC ACID DERIVATIVES AND OXYALKLENEGLYCOLALKENYL ETHERS, PROCESSES FOR THE PRODUCTION THEREOF AND USE THEREOF

Abstract The invention relates to copolymers based on unsaturated mono or dicarboxylic acid derivatives, oxyalkyleneglycol-alkenyl ethers, vinyl polyalkyleneglycol or ester compounds, in addition to the use thereof as additives for acqueous suspensions based on mineral or bituminous agents. Said invention is characterized in that the inventive copolymers, having a long lateral chain, impart small amounts of excellent processing properties to acqueous suspensions, and simultaneously, cause the water content in the concrete to be greatly reduced. Furthermore, the inventive copolymers cause, compared to prior art, dramatically increased early strength development which enables profitability, in particular in the construction of concrete, to be drastically increased.
Full Text Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and
oxyalkyleneglycol alkenyl ethers, processes for the production thereof and use thereof
Description
The present invention relates to copolymers based on unsaturated mon- or dicarboxylic acid*
derivatives and oxyalkyleneglycol alkenyl ethers, to processes for the production thereof and
to the use of these copolymers as additives for aqueous suspensions based on mineral or
bituminous binders.
The frequent addition of additives in the form of dispersing agents to aqueous suspensions of
hydraulic binders is known to improve the processability thereof, i.e. kneadability,
slumpability, sprayability, pumpability or flowability. These additives which usually contain
ionic groups are capable of breaking up solid agglomerated material, dispersing the resulting
particles and thus improving the processability specifically of highly concentrated
suspensions. This effect is specifically utilised in the production of building material mixtures
based on cement, lime and hydraulic binders based on calcium sulphate optionally also
admixed with organic (for example bituminous) fractions and also for ceramic materials,
refractory materials and oilfield building materials.
In order to convert these building material mixtures based on the aforementioned binders into
a processable form which is ready for use, substantially more mixing water is generally
necessary than would be required for the subsequent hydration or setting process. The hollow
proportion of the main body formed by the excess water which later evaporates results in
significantly impaired mechanical strength and resistance values.
In order to reduce this excess quantity of water with a predetermined processing consistency
and/or to improve the processability where there is a predetermined water/binder ratio,
additives are used which are generally termed water-reducing agents or fluidizers.
Polycondensation products based on naphthalene or alklynaphthalene sulphonic acids (cf.


EP-A 214 412) or melamine formaldehyde resins containing sulphonic acid groups (cf. DE-
PS 16 71 017) are predominantly known as agents of this type.
A disadvantage of these additives is the fact that the excellent liquefying action of which,
particularly in concrete construction, only lasts for a short period of time. The reduction in
processability of concrete mixtures ("slump-loss") within a short time can lead to problems
particularly where there is a long time interval between production and laying of the ready-
mixed concrete, for example conditioned by long conveying and transportation distances.
An additional problem arises from the use of such fluidizers in the mining industry and in the
internal field (gypsum plasterboard drying, anhydrite screed applications, production of
precast concrete parts), where the toxic formaldehyde contained in the products due to
production may be released, and thus workers' health may be seriously affected. It was for
this reason that attempts have already been made to instead develop formaldehyde-free
concrete fluidizers from maleic acid monoesters and styrene, for example according to EP-A
306 449. It is possible to maintain the flow action of concrete mixtures for a sufficiently long
period of time using these additives, although the originally present, very high dispersing
effect is lost very rapidly after storing the aqueous preparation of the fluidizer, caused by the
hydrolysis of the polymeric ester.
This problem does not occur in the case of fluidizers consisting of alkylpolyethleneglycol
allyl ethers and maleic acid anhydride corresponding to EP-A 373 621. However, these
products, as in the case as those described above, are surface-active compounds which
introduce, in an undesired manner, large quantities of air voids into the concrete mixture,
thereby resulting in a loss in the completeness and resistance of the hardened building
material.
Thus, it is necessary to add to the aqueous solutions of these polymer compounds antifoam
agents, for example tributylphosphate, silicone derivatives and various water-insoluble
alcohols in a concentration range of from 0.1 to 2 % by weight, based on the solids content.
Mixing in these components and maintaining a homogeneous form, which is stable in


storage, of the corresponding formulations proves to be extremely difficult even when these
antifoam agents are added in the form of emulsions.
It is possible to solve the problem of separation according to DE 195 13 126 Al by the
complete or at least partial incorporation of a defoaming or non-air introducing structural unit
into the copolymer.
It has been found, however, that the high efficiency and the low "slump-loss" of the
copolymers described here often results in unsatisfactory 24 hour strengths of the concrete.
Moreover, copolymers of this type do not exhibit the optimum properties particularly in cases
in which a particularly tightly joined, and thus high-strength and highly resistant, concrete is
to be produced with the smallest quantity of water possible and in which the intention is to
dispense with steam curing (prefabricated materials industry) in order to accelerate the
hardening process.
To solve this problem, DE 199 26 611 A1 proposed copolymers of unsaturated mono- or
dicarboxylic acid derivatives and oxyalkyleneglycol alkenyl ethers which are able to
maintain, for a period of time which meets practical requirements, the processability of
highly concentrated building material mixtures with low metering, for a strength, increased
simultaneously by an extreme reduction in the water/binder ratio, in the hardened state of the
building material. However, it has proved to be a disadvantage of these copolymers with
relatively short side chains that the early strength development of the corresponding building
material mixtures was less than optimum.
The present invention is therefore based on the object of providing new copolymers which do
not have the aforementioned disadvantages of the prior art, i.e., they are able to maintain the
processability of highly concentrated building material mixtures with a low dosing for a
period of time which meets practical requirements and simultaneously provide the
corresponding building materials with such high strength values after only a few hours that it
is possible to remove the formworks at an early stage and thus to reduce the cycle times in the
production of concrete parts in the casting plant or to significantly accelerate progress on the
building site.

This object was achieved according to the invention by the copolymers corresponding to
claim 1. In particular, it has surprisingly been found that the products according to the
invention based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkyleneglycol
alkenyl ethers with long side chains provide aqueous binder suspensions with outstanding
processing properties when added in the smallest amount and simultaneously cause a high
water reduction in the concretes. It was particularly surprising that it is possible due to the
extremely rapid development of strength to remove the concrete formworks after
unexpectedly short times and thus to drastically increase the economic efficiency in concrete
construction.
The copolymers according to the present invention contain at least three, but preferably four
structural groups a), b), c) and d). The first structural group a) is a mono- or dicarboxylic acid
derivative with the general formula Ia, Ib or Ic.

In the case of the monocarboxylic acid derivative Ia, R1 represents hydrogen or an aliphatic
hydrocarbon radical having from 1 to 20 C atoms, preferably a methyl group. X in the
structures Ia and Ib represents -OMa and/or -O-(CmH2mO)n-R2 or -NH-(CmH2mO)n-R2 wherein
M, a, m, n and R represent the following:
M represents hydrogen, a mono- or divalent metal cation (preferably sodium, potassium,
calcium or magnesium ion), ammonium, an organic amine radical and a = ½ or 1, depending
on whether M represents a mono- or divalent cation. Used as organic amine radicals are
preferably substituted ammonium groups derived from primary, secondary or tertiary C1-20-

alkylamines, C1-20 alkanolamines, C5-8 cycloalkylamines and C8-14 arylamines. Examples of
the corresponding amines include methylamine, dimethylamine, trimethylamine,
ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine,
dicyclohexylamine, phenylamine and diphenylamine in the protontated (ammonium) form.
R2 represents hydrogen, an aliphatic hydrocarbon radical having from 1 to 20 C atoms, a
cycloaliphatic hydrocarbon radical having from 5 to 8 C atoms, an aryl radical having from 6
to 14 C atoms which may optionally be substituted, m = 2 to 4 and n = 0 to 200. The aliphatic
hydrocarbon radicals may in this case be linear or branched and saturated or unsaturated.
Cyclopentyl or cyclohexyl radicals are considered as preferred cycloalkyl radicals and phenyl
or naphthyl radicals which may be substituted in particular by hydroxyl, carboxyl or
sulphonic acid groups are considered as preferred aryl radicals.
Instead of, or in addition to, the dicarboxylic acid derivative according to formula lb, the
structural group a) (mono- or dicarboxylic acid derivative) may also be present in cyclical
form corresponding to formula Ic, wherein Y = O (acid anhydride) or NR2 may represent
(acid imide) with the meaning denoted above for R2.
The second structural group b) corresponds to formula II

and is derived from oxyalkyleneglycol alkenyl ethers, wherein m' represents 2 to 4, n' + n"
represent 250 to 500 and p represents 0 to 3 and R2 and m respectively have the meaning
provided above.
R3 again represents hydrogen or an aliphatic hydrocarbon radical having from 1 to 5 C atoms
which may also be linear or branched or unsaturated.

According to the preferred embodiments, in formulae Ia, Ib and II, m represents 2 and/or 3,
so that polyalkylene oxide groups are concerned derived from polyethylene oxide and/or
polypropylene oxide. Moreover, in formula Ia, n may represent in particular 1 to 150. In a
further preferred embodiment, p in formula II represents 0 or 1, i.e. vinyl- and/or
allylpolyalkoxylates are concerned. In formula II, p particularly preferably represents 0 and m
represents 2.
The third structural group c) corresponds to formula IIIa or IIIb

In formula IIIa, R4 may represent H or CH3, depending on whether acrylic acid or
methacrylic acid derivatives are concerned. In this formula, Q may represent -H, -COOMa or
-COOR5 wherein a and M have the aforementioned meaning and R5 may be an aliphatic
hydrocarbon radical having from 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical
having from 5 to 8 C atoms or an aryl radical having from 6 to 14 C atoms. The aliphatic
hydrocarbon radical may also be linear or branched, saturated or unsaturated. The preferred
cycloaliphatic hydrocarbon radicals are again cyclopentyl or cyclohexyl radicals and the
preferred aryl radicals are phenyl or naphthyl radicals. When T = -COOR5, Q represents -
COOMa or -COOR5. When T and Q = -COOR5, the corresponding structural groups are
derived from the dicarboxylic acid esters.
The structural groups c) may also contain other hydrophobic structural elements in addition
to these ester structural units. Included among these are the polypropylene oxide or
polypropylene oxide-polyethylene oxide derivatives wherein


x assumes a value from 1 to 150 and y a value from 0 to 15. The polypropylene oxide
(polyethylene oxide) derivatives may in this case be linked via a grouping U1 with the ethyl
radical of structural group c) corresponding to formula IIIa, wherein U1 = -CO-NH-, -O- or
may be -CH2-O-. In this case, the corresponding amide-, vinyl- or allylether of the structural
group corresponding to formula IIIa is concerned. R6 may again be R2 (see above meaning of
R2), or

wherein U2 = -NH-CO-, -O-, or may represent -OCH2- and Q may have the meaning
described above. These compounds are polypropylene oxide(-polyethylene oxide) derivatives
of the bifunctional alkenyl compounds corresponding to formula IIIa.
As further hdroyphobic structural elements the structural groups c) may also contain
compounds according to formula IIIa wherein T = (CH2)Z-V-(CH2)Z-CH=CH-R2, wherein z =
0 to 4 and V may be a -O-CO-C6H4-CO-O radical and R2 has the aforementioned meaning. In
this case these are the corresponding difunctional ethylene compounds according to formula
IIIa which are linked together via ester groupings of formula -O-CO-C6H4-CO-O and wherein
only one ethylene group was copolymerised. These compounds are derived from the
corresponding dialkenyl-phenyl-dicarboxylic acid esters.
It is also possible within the scope of the present invention that not only one, but both
ethylene groups of the difunctional ethylene compounds were copolymerised. This
substantially corresponds to the structural groups corresponding to formula IIIb


wherein R2, V and z have the previously described meaning.
The fourth structural group d) is derived from an unsaturated dicarboxylic acid derivative of
the general formula IVa and/or IVb.

with the aforementioned meaning from a, M, X and Y.
It is to be considered as being fundamental to the invention that the copolymers contain from
25 to 98.99 mol % of structural groups of formula Ia and/or Ib and/or Ic, from 1 to 48.9 mol
% of structural groups of formula II, from 0.01 to 6 mol % of structural groups of formula
IIIa and/or IIIb and from 0 to 60 mol % of structural groups of formula IVa and/or IVb.
These polymers preferably contain from 70 to 94.98 mol % of structural groups or formula Ia
and/or Ib, from 5 to 25 mol % of structural groups of formula II, from 0.02 to 2 mol % of
structural groups of formula IIIa and/or IIIb and from 0 to 24.98 mol % of structural groups
of formula IVa and/or IVb.
According to a preferred embodiment, the copolymers of the invention also contain up to 50
mol %, in particular up to 20 mol % based on the total of structural groups a) to d), of
structures which are based on monomers based on vinyl- or (meth)acrylic acid derivatives,


such as styrene, α-methylstyrene, vinylacetate, vinylpropionate, ethylene, propylene,
isobutene, N-vinylpyrrolidone, allylsulphonic acid, methallylsulphonic acid, vinylsulphonic
acid or vinylphosphonic acid.
Preferred monomelic (meth)acrylic acid derivatives include hydroxyalkyl(meth)acrylates,
acrylamide, methacrylamide, AMPS, methylmethacrylate, methlyacrylate, butylacrylate or
cyclohexylacrylate.
The number of recurring structural units in the copolymers is not restricted. However, it has
proved to be particularly advantageous to adjust average molecular weights of from 1,000 to
100,000 g/mol.
The copolymers according to the invention may be produced in different ways. It is
fundamental here that from 25 to 98.99 mol % of an unsaturated mono- or dicarboxylic acid
derivative, from 1 to 48.9 mol % of an oxyalkylene-alkenyl ether, from 0.01 to 6 mol % of a
vinyl polyalkyleneglycol compound or ester compound and from 0 to 60 mol % of a
dicarboxylic acid derivative are polymerised using a radical initiator.
Acrylic acid, methacrylic acid, itaconic acid, itaconic acid anhydride, itaconic acid imide and
itaconic acid monoamide are preferably used as unsaturated mono- or dicarboxylic acid
derivatives forming the structural groups of formula Ia, Ib or Ic.
Instead of acrylic acid, methacrylic acid, itaconic acid and itaconic acid monoamide, the
mon- or divalent metal salts thereof may also be used, preferably sodium, potassium, calcium
or ammonium salts.
As acrylic, methacrylic or itaconic acid esters, derivatives are predominantly used, the
alcoholic component of which is a polyalkyleneglycol of the general formula HO-
(CmH2mO)n-R2 wherein R2 = H, an aliphatic hydrocarbon radical having from 1 to 20 C
atoms, a cycloaliphatic hydrocarbon radical having from 5 to 8 C atoms, an optionally
substituted aryl radical having from 6 to 14 C atoms and wherein n = 2 to 4 and m = 0 to 200.

The preferred substituents on the aryl radical are -OH-, -COO- or -SO3- groups.
The unsaturated monocarboxylic acid derivatives may be present only as monoesters,
whereas in the case of dicarboxylic acid and itaconic acid, diester derivatives are also
possible.
The derivatives of formulae Ia, Ib and Ic may also be present as a mixture of esterified and
free acids and are used in a quantity of preferably from 70 to 94.98 mol %.
The second component, fundamental to the invention, for the production of the copolymers of
the invention is an oxyalkyleneglycol-alkenyl ether which is preferably used in a quantity of
from 5 to 25 mol %. In the preferred oxyalkyleneglycol alkenyl ethers corresponding to
formula V

R3=H or an aliphatic hydrocarbon radical having from 1 to 5 C atoms, m' = 2 to 4, n' + n" =
from 250 to 500 and p = 0 to 3. R2, m and n have the aforementioned meaning. In this case,
the use of polyethyleneglycolmonovinylether (p = 0 and m = 2) has proved to be particularly
advantageous, wherein n preferably has values between 1 and 50.
As the third component, fundamental to the invention, for introducing the structural group c),
from 0.02 to 2 mol % of a vinylpolyalkyleneglycol compound or ester compound are
preferably used. As preferred vinyl polyalkyleneglycol compounds, derivatives
corresponding to formula VI are used,


wherein Q may preferably be -H, or -COOMa, R4 = -H, CH3 and U1 = -CO-NH-, -O- or -
CH2O-, i.e. the acid amide ethers, vinyl ethers or allyl ethers of the corresponding
polypropyleneglycol or polypropyleneglycol-polyethyleneglycol derivatives are concerned.
The values for x are 1 to 150 and for y are 0 to 15. R6 can either again be R2 or may represent

wherein U2 = -NH-CO-, -O- and -OCH2- and Q = -COOMa and is preferably -H.
When R6 = R2 and R2 preferably represents H, the polypropylene glycol
(polyethyleneglycol)-monoamides or ethers of the corresponding acrylic (Q = H, R4 = H),
methacrylic (Q = H, R4 = CH3) or maleic acid (Q = -COOMa-R4 = H) derivatives are
concerned. Examples of such monomers include maleic acid-N-(methylpolypropyleneglycol)
monoamide, maleic acid-N-(methoxy-polypropyleneglycol-polyethyleneglycol) monoamide,
polypropyleneglycol vinylether and polypropyleneglycol allylether.
When R6 ≠ R , bifunctional vinyl compounds are concerned, the polypropyleneglycol-
(polyethyleneglycol) derivatives thereof are linked together via amide or ether groups in (-0-
or -OCH2-)- Examples of such compounds include polypropyleneglycol-bis-maleic acid
amide, polypropyleneglycoldiacrylamide, polypropyleglycoldimethacrylamide,
polypropyleneglycol divinylether and polypropyleneglycoldiallylether.
Derivatives corresponding to the following formula VII are preferably used as a vinylester
compound within the scope of the present invention:


wherein Q = -COOMa or -COOR5 and R5 may be an aliphatic hydrocarbon radical having
from 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having from 5 to 8 C atoms and
an aryl radical having from 6 to 14 C atoms, a and M have the aforementioned meaning.
Examples of such ester compounds include di-n-butylmaleinate or fumarate or mono-n-
butylmaleinate or fumarate.
Furthermore, compounds corresponding to formula VIII may also be used

wherein z may again be 0 to 4 and R2 has the aforementioned meaning. In this formula, V
represents -0-CO-C6H4-CO-O-. For example, these compounds are dialkenylphthalic acid
derivatives. A typical example of phthalic acid derivatives of this type is diallyphthalate.
The molecular weights of the compounds forming structural group c) may be varied within
wide limits and are preferably between 150 and 10,000.
From 0 to 24.98 mol % of an unsaturated dicarboxylic acid derivative IX may preferably be
used as the fourth component for the production of the copolymers according to the
invention:


with the aforementioned meaning for a, M and X.
When X = OMa, the unsaturated dicarboxylic acid derivative is derived from maleic acid,
fumaric acid, mono- or divalent metal salts of these dicarboxylic acids, such as the sodium,
potassium, calcium or ammonium salt or salts with an organic amine radical. Monomers
which are also used and which form the unit Ia are polyalkyleneglycolmonesters of the
aforementioned acids with the general formula X

with the aforementioned meaning for a, m, n and R2.
The fourth component may also be derived from the unsaturated dicarboxylic acid anhydrides
and imides of the general formula XI

with the aforementioned meaning for Y.
According to a preferred embodiment, up to 50, preferably up to 20 mol %, based on the total
of structural groups a) to d), of other monomers may be used according to the invention as
described above.
The copolymers according to the present invention may be produced by conventional
methods. A particular advantage is that it is possible according to the invention to work


without solvent or else in aqueous solution. Both cases involve pressureless and thus safty-
related reactions.
If the process is carried out in aqueous solution, polymerisation takes place at from 20 to 100
°C using a conventional radical initiator, the concentration of the aqueous solution preferably
being set at 30 to 50 % by weight. According to a preferred embodiment, the radical
polymerisation may be carried out in the acid pH range, in particular at a pH of between 4.0
and 6.5, wherein the conventional initiators, such as H2O2, may be used without resulting in
separation of ether as feared, which would have a considerably adverse effect on the yields.
The process according to the invention is preferably carried out so that the unsaturated
dicarboxylic derivative forming the structural group d) is introduced in partly neutralised
form in aqueous solution, preferably together with the polymerisation initiator and the
remaining monomers are added as soon as the receiver reaches the necessary reaction
temperature. Added separately are the polymerisation auxiliaries which are able to lower the
activation threshold of the preferably peroxidic initiator, so that copolymerisation can take
place at relatively low temperatures. According to another preferred embodiment, the
unsaturated dicarboxylic acid derivative as well as the radical former may also be added in
separate or joint inlets of the reactor receiver, which ideally solves the problem of heat
dissipation.
On the other hand, it is also possible to introduce the polyoxyalkyleneglycol alkenylethers
forming structural group b) and to add the mono- or dicarboxylic acid derivative (structural
group a)), so that a uniform distribution of the monomer units over the polymer chain is
achieved.
The type of polymerisation initiators, activators and other auxiliaries which are used, for
example molecular weight controllers, is relatively straight forward, i.e. the initiators used are
the conventional radical donors such as hydrogen peroxide, sodium, potassium or ammonium
peroxodisulphate, tert. butylhydroperoxide, dibenzoylperoxide, sodium peroxide, 2,2'-azobis-
(2-amidinopropane)-dihydrochloride, azobis-(isobutyronitrile), etc. If redox systems are used,
the abovementioned initiators are combined with reducing activators. Examples of such


reducing agents include Fe(II)-salts, sodiumhydroxymethanesulphinatedihydrate, alkali
metalsulphites and metabisulphites, sodium hypophosphite, hydroxylaminehydrochloride,
thiourea, etc.
A particular advantage of the copolymers according to the invention is the fact that they may
also be produced without solvent, and this may be carried out using the conventional radical
initiators at temperatures between 20 and 150 °C. This variant may be employed for
economic reasons particularly when the copolymers according to the invention in anhydrous
form are to be directly supplied for the use thereof according to the invention, as it is then
possible to dispense with a costly separation of the solvent, in particular water (for example
by spray drying).
The copolymers according to the invention are outstandingly suitable as an additive for
aqueous suspensions of organic and inorganic solids based on mineral or bituminous binders,
such as cement, gypsum, lime, anhydrite or other building materials based on calcium
sulphate, or based on powder dispersion binders, in which case they are used in a quantity of
0.01 to 10 % by weight, in particular from 0.051 to 5 % by weight, based on the weight of the
mineral binder.
The following examples are provided to explain the invention in more detail.
Examples
Synthesis and use examples
Example 1
A solution consisting of 310 g (0.0258 mol) of vinyloxybutyl-poly-(ethyleneglycol) [average
molecular weight 12,000 g/mol] and 350 g of water are introduced at room temperature into a
1 litre double-walled reaction vessel equipped with thermometer, stirrer, pH meter and two
inlets for separate feeds.


Outside the reaction vessel, 23.81 g (0.33 mol) acrylic acid and 0.256 g (0.000142 mol) of a
monofunctional NH2-terminated ethylene oxide/propylene oxide-block copolymer (EO4,
PO27; molecular weight 1,800 g/mol) = α-butyl-ω-(maleinamido)-poly-(ethyleneglycol)-
block-poly(propyleneglycol) started on butanol were diluted with 61.91 g of water.
38.2 g of the acrylic acid-water mixture were added with vigorous stirring and cooling to the
vinylpolyether-water solution, followed by a waiting period until the starting temperature of
15 °C was again reached. Thereafter, 0.059 g of iron(II) sulphate-heptahydrate and 0.3 g of 3-
mercaptopropanoic acid were added and the pH was adjusted to 5.3 using a 20 % NaOH
solution. The reaction was started by adding 1.5 g of 30 % aqueous hydrogen peroxide. 40.38
g of the acrylic acid solution, to which 3.4 g of 3-mercaptopropanoic acid had been added,
were added over a period of 30 minutes. 10 ml of a 6 % aqueous solution of Briiggolit™
were added separately within 40 minutes.
After the addition, the solution was adjusted, with stirring, to a pH of 6.5 by adding 24.1 ml
of a 20 % sodium hydroxide solution. The faintly yellowish coloured, cloudy aqueous
polymer solution contained 42.5 % of solids. The average molecular weight of the copolymer
was 65,700 g/mol.
Example 2
Example 1 was repeated, but instead of using the vinyloxybutyl-poly(ethyleneglycol) [MW
12,000 g/mol] of that example, a polyether having an average molecular weight of 20,000
g/mol was used.
The example was based on the following required quantities:
16.13 g (0.224 mol) acrylic acid
350.00 g (0.0175 mol) vinyloxybutyl-poly-(ethyleneglycol)
0.18 g (0.0001 mol) α-butyl-ω-(maleinamido)-poly-(ethyleneglycol)-block-poly-
(propyleneglycol)


A light yellow, cloudy aqueous polymer solution was obtained having an average molecular
weight of 72,300 g/mol.
Example 3
The same process was carried out as described in Example 1, except with a significantly
increased amount of acrylic acid of 47.62 g (0.66 mol). All the other monomers were used in
the same amounts as in Example 1.
After neutralisation with aqueous sodium hydroxide solution, a copolymer solution having an
average molecular weight of 60,800 g/mol was obtained.
Example 4
The amount of acrylic acid used in Example 1 was reduced to a third of the amount used
there, i.e. 7.94 g (0.11 mol). A pale yellow polymer solution was obtained having a molecular
weight of 58,700 g/mol.
Example 5
A copolymer was synthesised from the following monomers by the process described in
Example 1:
23.81 g (0.33 mol) acrylic acid
310.00 g (0.026 mol) vinyloxybutyl-poly-(ethyleneglycol) with MW = 12,000 g/mol
7.42 g (0.034 mol) maleic acid-dibutylester
49.0 g (0.50 mol) maleic acid anhydride
The resulting brownish aqueous copolymer had an average molecular weight of 36,900
g/mol.


Example 6
Analogously to Example 1, a copolymer was synthesised which contained 21.84 g (0.195
mol) of itaconic acid anhydride instead of the acrylic acid used in Example 1. The average
molecular weight of the end product was 42,300 g/mol.
Example 7
Example 1 was repeated. In addition to the monomers used therein,
123.2 g (0.112 mol) methylpoly(ethyleneglycol)-methacrylate (MW = 1100 g/mol)
were introduced into the reactor solution together with the acrylic acid/water mixture.
The slightly cloudy aqueous reaction product had an average molecular weight of 69,300
g/mol.
Example 8
A copolymer (MW 60,000 g/mol) was produced by the process described in Example 1, a
mixture of methacrylic acid and acrylic acid (in each case 0.165 mol) was used instead of the
acrylic acid.
Example 9
Instead of the vinyloxybutyl-poly(ethyleneglycol) used in Example 1 having an average
molecular weight of 12,000 g/mol, a mixture of 2 vinylethers was used:
Component 1: 204 g (0.017 mol) vinlypolyether-12000
Component 2: 68 g (0.034 mol) vinylpolyether-2000 (vinyloxybutyl-PEG with an
average MW of 2000 g/mol)


The two components were mixed with 300 g of water in the receiver. The resulting
copolymer had a weight- average molecular weight 59,900 g/mol.
Example 10
In addition to the vinylether used in Example 1
5.2 g (0.05 mol) of styrene
were introduced together with the vinylether. The resulting very cloudy aqueous polymer
solution was odour free and had an average molecular weight of 70,600 g/mol.
Example 11 to 14
The following compounds were used instead of the EO/PO-adduct (copolymer constituent
III) used in Example 1:
Example 11
0.426 g (0.000213 mol) α,ω-bis-(maleinamido)-poly-(propyleneglycol) (MW 2000
g/mol)
Example 12
0.254 g (0.000169 mol) methyl-poly-(ethyleneglycol)-block-poly-(propyleneglycol)-
allylether (MW = 1500 g/mol, E04, P022)
Example 13
0.5 g (0.00025 mol) α,ω-bis-(methacryloyloxy)-poly-(propyleneglycol) with MW =
2000 g/mol
Example 14
4.674 g (0.019 mol) phthalic acid diallylester

Example 15
The following compound was used instead of the vinyl ether used in Example 1:
260 g (0.02 mol) vinyloxybutyl-polyether-(propyleneglycol)-block-poly-
(ethyleneglycol) [P0 25, E0 250) with MW = 13,000 g/mol.
The resulting yellowish, very cloudy polymer solution had a molecular weight of 70,300
g/mol.
Example 16
Example 1 was repeated, except that
85.8 g (0.66 mol) hydroxypropylacrylate
were also introduced in addition to the acrylic acid.
The resulting copolymer had a weight- average molecular weight of 74,700 g/mol.
Molar composition of the copolymers according to the invention:



1) Mixture of acrylic acid and MPEG methacrylate-1100 (3:1)
2) Mixture of acrylic acid and methacrylic acid (1:1)
3) Mixture of VOBPEG-12000 and VOBPEG-2000 (1:2)
4) Styrene
5) Mixture of acrylic acid and hydroxypropylacrylate (1 : 2)
Comparative example
Commercially available high-performance fluidizer (as in PCT/EP00/02251) Glenium ACE
30 produced by Degussa AG
Use examples
Prefabricated concrete application
10 kg of Portland cement (Bernburger CEM 1 52,5 R (ft)) were mixed according to standards
in a concrete forced mixer with 47.2 kg of aggregates (grading curve 0 to 16 mm) and 3.6 kg
of water (including the water from the additive). The aqueous solutions of the product
according to the invention and of the comparative product respectively were added and the
slump was determined according to DIN EN 12350-5 4 and 40 minutes respectively after the
beginning of the test.
Table 1 summarises the composition of the concrete mixture:
Table 1:


Following measurement of the slump, samples with edge lengths of 15x 15x 15 cm were
produced and stored at 20 °C. The compressive strength was determined after 6, 8 and 10
hours. The air void content of the samples was 1.6 % by volume.
The results are provided in Table 2:

4.3 kg of Portland cement (Bernburger CEM 1 52,5 R (ft)) were mixed according to
standards in a concrete forced mixer with 20.1 kg of aggregates (grading curve 0. to 16 mm)

and 1.6 kg of water (including the water from the additive). The aqueous solutions of the
product according to the invention and of the comparative product respectively were added
and the slump was determined according to DIN EN 12350-5 4 minutes after the start of the
test.
Table 3 summarises the composition of the concrete mixture:
Table 3:

Following measurement of the slump, samples having an edge length of 10 x 10 x 10 cm
were produced and stored at 10 °C. The compressive strength was determined after 10, 12
and 16 hours. The air void content of the samples was 1.6 % by volume.
The results are provided in Table 4:




WE CLAIM:
1. Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and
oxyalkylenegycol-alkenyl ethers, characterized in that they contain
a) from 25 to 98.99 mol % of the structural groups of formula la

wherein R1 represents hydrogen or an aliphatic hydrocarbon radical having from
1 to 20 C atoms
X represents -OMa, -O-(CmH2mO)n-R2, NH-(CmH2mO)nR2
M represents hydrogen, a mono-or divalent metal cation, ammonium ion,
an organic amine radical,
a represents ½ or 1
R2 represents hydrogen, an aliphatic hydrocarbon radical having from 1 to
20 C atoms, a cycloaliphatic hydrocarbon radical having from 5 to 8 C
atoms, an optionally substituted aryl radical having from 6 to 14 C atoms
m represents 2 to 4, and
n represents 0 to 200,
b) from 1 to 48.9 mol % of the structural group of general formula II


wherein R3 represents hydrogen or an aliphatic hydrocarbon radical having from 1
to 5 C atoms,
m' represents 2 to 4
n' + n" represent 250 to 500
p represents 0 to 3, and
R2 and m have the above-mentioned meaning,
c) from 0.01 to 6 mol % of structural groups of formula IlIa or IIIb

-COOR5 when Q represents -COOR5 or -COOMa
U1 represents -CO-NH-, -O-, CH2O-
U2 represents-NH-CO-, -O-, -OCH2-
V represents -O-CO-C6H4-CO-O
R4 represents H, CH3

R5 represents an aliphatic hydrocarbon radical having from 3 to 20 C
atoms, a cycloaliphatic hydrocarbon having from 5 to 8 C atoms, an aryl
radical having from 6 to 14 C atoms
R6=R2,

z represents 0 to 4
x represents 1 to 150
y represents 0 to 15,
and
d) from 0 to 60 mol of structural groups of general formula IVa and/or IVb

with the above mentioned meaning for a, M, X, and Y.

2. Copolymers as claimed in claim 1, wherein R1 represents a methyl radical.
3. Copolymers as claimed either claim 1 or claim 2, wherein M represents a mono-
or divalent metal cation selected from the group of sodium, potassium, calcium or
magnesium ions.
4. Copolymers as claimed in any one of claims 1 to 3, wherein when R2 represents
phenyl, the phenyl radical is further substituted by hydroxyl, carboxyl or sulphonic
acid groups.
5. Copolymers as claimed in any one of claims 1 to 4, wherein in formula la n
represents 1 to 150.
6. Copolymers as claimed in any one of claims 1 to 5, wherein in formula II, p
represents 0 and m represents 2.
7. Copolymers as claimed in any one of claims 1 to 6, wherein that they contain
from 70 to 94.98 mol% of structural groups of formula la and/or lb andor Ic, from
5 to 25 mol% of structural groups of formula II, from 0.02 to 2 mol% of structural
groups of formula IlIa and/or lllb and from 0 to 24.98 mol% of structural groups of
formula IVa and/or IVb.
8. Copolymers as claimed in any one of claims 1 to 7, wherein that they also
contain up to 50mol%, in particular up to 20mol%, based on the total of the
structural groups of formulae I, II, III and IV, of structural groups, the monomers
of which represent a vinyl or (meth) acrylic acid derivative.

9. Copolymers as claimed in claim 8, wherein that styrene, a-methlystryrene, vinyl
acetate, vinyl propionate, ethylene, propylene, isobuteane, N-vinylpyrrolidone,
allylsulphonic acid, methallylsulphonic acid, vinyl sulphonic acid or vinyl
phosphonic acid are used as the monomeric vinyl derivative.
10. Copolymers as claimed in claim 9, wherein that hydroxyalkyl (meth) acrylate,
acrylamide, methacrylalmide, AMPS, methylmethacylate, methylacrylate,
butylacrylate or cyclohexylacrylate are used as the monomeric (meth) acrylic acid
derivative.
11. Copolymers as claimed in any one in claims 1 to 10, wherein that they have an
average molecular weight of from 1,000 to 100,000 g/mol.
12. Process for the production of the copolymers as claimed in any one in claims 1 to
11, wherein that from 25 to 98.99 mol% of an unsaturated mono- or diocarboxylic
acid derivative, from 1 to 48.9 mol% of an oxyalkyleneglycol alkenylether, 0.01 to
6 mol% of a vinyl polyalkyleneglycol compound or ester compound and from 0 to
60 mol% of a dicarboxylic acid derivative are polymerized using a radical initiator.
13. Process as claimed in claim 12, wherein that from 70 to 94.88 mol% of an
unsaturated mono- or diocarboxylic acid derivative, from 5 to 25 mol% of an
oxyalkyleneglycol alkenylether, from 0.02 to 2 mol% of a vinyl polyalkyleneglycol
compound or ester compound and from 0 to 24.98 mol% of a dicarboylic acid
derivative are used.
14. Process as claimed either in claim 12 or claim 13, wherein that up to 50 mol% in
particular up to 20 mol%, based on the monomers with the structural groups
according to the formulae I, II, III and V, of a vinyl- or (meth)acrylic acid derivative
are also copolymerized.

15. Process as claimed in any one of claims 12 to 14, wherein that polymerization is
carried out in aqueous solution at a temperature of from 20 to 100 °C.
16. Process as claimed in any one of claim 15, wherein that the concentration of the
aqueous solution is from 30 to 50% by weight.
17. Process as claimed in any one of claims 12 to 14, wherein that polymerization is
carried out without solvent using a radical initiator at temperature of from 20 to
150 °C.


The invention relates to copolymers based on unsaturated mono or dicarboxylic acid
derivatives, oxyalkyleneglycol-alkenyl ethers, vinyl polyalkyleneglycol or ester
compounds, in addition to the use thereof as additives for acqueous suspensions based
on mineral or bituminous agents. Said invention is characterized in that the inventive
copolymers, having a long lateral chain, impart small amounts of excellent processing
properties to acqueous suspensions, and simultaneously, cause the water content in
the concrete to be greatly reduced. Furthermore, the inventive copolymers cause,
compared to prior art, dramatically increased early strength development which enables
profitability, in particular in the construction of concrete, to be drastically increased.

Documents:

02134-kolnp-2006-abstract-1.1.pdf

02134-kolnp-2006-abstract.pdf

02134-kolnp-2006-assignment.pdf

02134-kolnp-2006-claims-1.1.pdf

02134-kolnp-2006-claims.pdf

02134-kolnp-2006-correspondence other.pdf

02134-kolnp-2006-correspondence others-1.1.pdf

02134-kolnp-2006-correspondence-1.2.pdf

02134-kolnp-2006-correspondence-1.3.pdf

02134-kolnp-2006-description (complete).pdf

02134-kolnp-2006-form-1.pdf

02134-kolnp-2006-form-2.pdf

02134-kolnp-2006-form-26..pdf

02134-kolnp-2006-form-3.pdf

02134-kolnp-2006-form-5-1.1.pdf

02134-kolnp-2006-form-5.pdf

02134-kolnp-2006-international publication.pdf

02134-kolnp-2006-international search authority report-1.1.pdf

02134-kolnp-2006-international search authority report-1.2.pdf

02134-kolnp-2006-international search report.pdf

02134-kolnp-2006-p.a.pdf

02134-kolnp-2006-pct form.pdf

02134-kolnp-2006-priority document-1.1.pdf

02134-kolnp-2006-priority document.pdf

2134-KOLNP-2006-(21-09-2012)-CORRESPONDENCE.pdf

2134-KOLNP-2006-(27-04-2012)-CORRESPONDENCE.pdf

2134-KOLNP-2006-ABSTRACT.pdf

2134-kolnp-2006-assignment.pdf

2134-KOLNP-2006-CLAIMS.pdf

2134-KOLNP-2006-CORRESPONDENCE 1.1.pdf

2134-KOLNP-2006-CORRESPONDENCE 1.3.pdf

2134-kolnp-2006-correspondence-1.2.pdf

2134-KOLNP-2006-CORRESPONDENCE.pdf

2134-KOLNP-2006-DESCRIPTION (COMPLETE).pdf

2134-KOLNP-2006-ENGLISH TRANSLATION.pdf

2134-KOLNP-2006-EXAMINATION REPORT REPLY RECIEVED.pdf

2134-kolnp-2006-examination report.pdf

2134-KOLNP-2006-FORM 1 1.2.pdf

2134-KOLNP-2006-FORM 1 1.3.pdf

2134-kolnp-2006-form 1-1.4.pdf

2134-KOLNP-2006-FORM 1.1.1.pdf

2134-KOLNP-2006-FORM 1.pdf

2134-KOLNP-2006-FORM 13.pdf

2134-kolnp-2006-form 18.pdf

2134-KOLNP-2006-FORM 2 1.3.pdf

2134-KOLNP-2006-FORM 2.1.1.pdf

2134-KOLNP-2006-FORM 2.pdf

2134-kolnp-2006-form 26.pdf

2134-KOLNP-2006-FORM 3 1.3.pdf

2134-kolnp-2006-form 3-1.4.pdf

2134-KOLNP-2006-FORM 3.1.1.pdf

2134-KOLNP-2006-FORM 3.1.2.pdf

2134-KOLNP-2006-FORM 3.pdf

2134-KOLNP-2006-FORM 5 1.3.pdf

2134-kolnp-2006-form 5-1.4.pdf

2134-KOLNP-2006-FORM 5.1.1.pdf

2134-KOLNP-2006-FORM 5.pdf

2134-kolnp-2006-form 6-1.1.pdf

2134-kolnp-2006-form 6.pdf

2134-KOLNP-2006-FORM-27.pdf

2134-kolnp-2006-granted-abstract.pdf

2134-kolnp-2006-granted-claims.pdf

2134-kolnp-2006-granted-description (complete).pdf

2134-kolnp-2006-granted-form 1.pdf

2134-kolnp-2006-granted-form 2.pdf

2134-kolnp-2006-granted-specification.pdf

2134-KOLNP-2006-OTHERS 1.3.pdf

2134-KOLNP-2006-OTHERS DOCUMENTS.pdf

2134-kolnp-2006-others-1.4.pdf

2134-KOLNP-2006-OTHERS.pdf

2134-KOLNP-2006-PETITION UNDER RULE 137.pdf

2134-kolnp-2006-reply to examination report.pdf


Patent Number 247494
Indian Patent Application Number 2134/KOLNP/2006
PG Journal Number 15/2011
Publication Date 15-Apr-2011
Grant Date 12-Apr-2011
Date of Filing 28-Jul-2006
Name of Patentee M/S CONSTRUCTION RESEARCH & TECHNOLOGY GMBH
Applicant Address DR. SLBERT FRANK-STR. 32, 83308 TROSTBERG
Inventors:
# Inventor's Name Inventor's Address
1 MORARU, BOGDAN PRINZREGENTENSTR. 63, 83022 ROSENHEIM
2 ALBRECHT, GERHARD JAGERWEG 7A, 83342 TACHERTING
3 SCHEUL, STEFANIE LINDACHER STR. 43, 83308 TROSTBERG
4 JETZLSPERGER, EVA PETER-DORFLER-STR. 12 84579 UNTERNEUKIRCHEN
5 HUBSCH, CHRISTIAN UNTERZACHERL 6, 83703 GMUND
PCT International Classification Number C08F 220/10
PCT International Application Number PCT/EP2005/001087
PCT International Filing date 2005-02-03
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2004 005 434.7 2004-02-04 Germany